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Electron hopping and charge separation within a naphthalene-1,4:5,8-bis(dicarboximide) chiral covalent organic cage

Solomek, Tomas, Powers-Riggs, Natalia E., Wu, Yi-Lin, Young, Ryan M., Krzyaniak, Matthew D., Horwitz, Noah E. and Wasielewski, Michael R. 2017. Electron hopping and charge separation within a naphthalene-1,4:5,8-bis(dicarboximide) chiral covalent organic cage. Journal of the American Chemical Society 139 (9) , pp. 3348-3351. 10.1021/jacs.7b00233

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Abstract

We present the stereoselective synthesis of a chiral covalent organic cage consisting of three redox-active naphthalene-1,4:5,8-bis(dicarboximide) (NDI) units by dynamic imine chemistry. Single crystal X-ray diffraction analysis shows that host–guest interactions and racemic cocrystallization allow for controlling the solid state structure. Electronic interactions between the NDI units probed by absorption and circular dichroism spectroscopies, electrochemistry and theoretical calculations are shown to be weak. Photoexcitation of NDI leads to intracage charge separation with a longer lifetime than observed in the corresponding monomeric NDI and dimeric NDI cyclophane imines. The EPR spectrum of the singly reduced cage shows that the electron is localized on a single NDI unit at ambient temperatures and transitions to rapid hopping among all three NDI units upon heating to 350 K. Dynamic covalent chemistry thus promises rapid access to covalent organic cages with well-defined architectures to study charge accumulation and electron transport phenomena.

Item Type: Article
Date Type: Publication
Status: Published
Schools: Chemistry
Publisher: American Chemical Society
ISSN: 0002-7863
Date of First Compliant Deposit: 16 January 2019
Date of Acceptance: 22 February 2017
Last Modified: 25 Nov 2020 06:27
URI: http://orca-mwe.cf.ac.uk/id/eprint/118416

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